US20160093824A1 - Interface layer for electronic devices - Google Patents

Interface layer for electronic devices Download PDF

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US20160093824A1
US20160093824A1 US14/392,111 US201414392111A US2016093824A1 US 20160093824 A1 US20160093824 A1 US 20160093824A1 US 201414392111 A US201414392111 A US 201414392111A US 2016093824 A1 US2016093824 A1 US 2016093824A1
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layer
tco
interface layer
electrode
underlayers
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US9716243B2 (en
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Neil Mcsporran
Gary Robert Nichol
David Alan Strickler
Kevin David Sanderson
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Pilkington Group Ltd
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/805—Electrodes
    • H10K50/81—Anodes
    • H01L51/5206—
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • C03C17/245—Oxides by deposition from the vapour phase
    • C03C17/2453—Coating containing SnO2
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • C03C17/245—Oxides by deposition from the vapour phase
    • C03C17/2456—Coating containing TiO2
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/153—Constructional details
    • G02F1/155—Electrodes
    • H01L51/5234—
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/805—Electrodes
    • H10K50/81—Anodes
    • H10K50/814—Anodes combined with auxiliary electrodes, e.g. ITO layer combined with metal lines
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/805—Electrodes
    • H10K50/82—Cathodes
    • H10K50/828—Transparent cathodes, e.g. comprising thin metal layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/10—Transparent electrodes, e.g. using graphene
    • H10K2102/101—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO]
    • H10K2102/102—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO] comprising tin oxides, e.g. fluorine-doped SnO2

Definitions

  • the invention concerns an interface layer for incorporation in devices produced on a transparent, electrically conducting electrode.
  • a number of electrical devices are known which are concerned with the generation or modification of light and which comprise an active region located between two essentially planar electrodes.
  • an active region located between two essentially planar electrodes.
  • at least one electrode must be transparent.
  • Such devices include organic light emitting diodes (OLED) and electrochromic devices.
  • an emissive electroluminescent layer comprising one or more layers of organic compound is located between the electrodes and emits light in response to an applied voltage.
  • electrochromic devices In electrochromic devices a stack of materials which, in combination exhibit electrochromic properties is located between the electrodes and changes colour and, or opacity in response to an applied voltage.
  • Devices of the type which concern the invention are typically fabricated by providing a transparent conducting electrode comprising a transparent substrate and a conductive coating stack, and building successive layers thereon comprising the active region of the device and a further electrode—which may also be transparent.
  • the transparent conducting electrode is frequently realised by depositing the conductive stack of coatings on the substrate using techniques such as chemical vapour deposition (CVD), which are well known to persons skilled in the art, see for example U.S. Pat. No. 7,968,201.
  • CVD chemical vapour deposition
  • the conductive stack typically comprises a Transparent Conducting Oxide (TCO), i.e. a doped metal oxide, as the uppermost layer (i.e. the furthest layer from the substrate).
  • TCO Transparent Conducting Oxide
  • the TCO should offer a suitable surface for deposition of further layers as the rest of the device is fabricated.
  • transparent conductive oxide materials include fluorine doped tin oxide (SnO 2 :F), Zinc oxide doped with Aluminium, Gallium or Boron (ZnO:Al, ZnO:Ga, ZnO:B), Indium oxide doped with tin (ITO) and cadmium stannate.
  • the current invention addresses both of these problems.
  • a transparent electrode comprises the features set out in claim 1 attached hereto.
  • the inventors have shown that incorporation of a thin interface layer between the top of the electrode stack (TCO) and the active region of the device overcomes problems associated with roughness of the TCO.
  • interface layer materials include TiO 2 , SiO 2 , SnO 2 and ZnO and mixtures comprising any of these. The good device performance obtained when such interface layers are included is surprising because these materials have high electrical resistance.
  • the interface layer comprises a TiO 2 layer having a thickness greater than 5 nm.
  • the interface layer comprises ZnO, having a thickness between 25 and 80 nm.
  • the TCO layer comprises a fluorine doped tin oxide.
  • the underlayers comprise a layer of SnO 2 and a layer of SiO 2 .
  • the transparent conducting electrode according to the invention is suitable for incorporation in electronic devices such as electrochromic devices and organic light emitting diodes.
  • a method of manufacturing a transparent conducting electrode comprises the steps set out in claim 8 attached hereto.
  • the underlayers, TCO and interface layer are deposited by Chemical Vapour Deposition (CVD).
  • the CVD may be done on the float glass ribbon produced during the float glass production process.
  • the underlayers, TCO and interface layer are deposited by Plasma Enhanced CVD.
  • the underlayers, TCO and interface layer are deposited by sputtering.
  • the interface layer is selected from TiO 2 , SiO 2 and ZnO. More preferably, the interface comprises TiO 2 having a thickness of less than 5 nm.
  • the interface layer comprises ZnO, having a thickness between 25 and 80 nm.
  • the TCO layer comprises a fluorine doped tin oxide.
  • the underlayers comprise a layer of SnO 2 and a layer of SiO 2 .
  • the stack comprising at least one underlayer and a transparent conducting oxide (TCO) layer located on the underlayers, is characterised by the electrode having an interface layer located on the transparent conducting oxide layer.
  • TCO transparent conducting oxide
  • FIG. 1 shows a transparent conducting electrode of the prior art
  • FIG. 2 shows an electrochromic device incorporating a transparent conducting electrode according to the invention
  • FIG. 3 shows an organic light emitting diode incorporating a transparent conducting electrode according to the invention
  • FIG. 4 illustrates a so-called ‘dynamic coater’ used for laboratory scale chemical vapour deposition of coatings on a substrate.
  • a transparent conducting electrode of the type concerned by the invention typically comprises a glass substrate 1 bearing a conductive stack of coatings 2 , 3 and 4 .
  • the stack comprises underlayers of SnO 2 2 and SiO 2 3 and a TCO layer 4 of SnO 2 :F.
  • the TCO layer 4 typically has a rough surface (although the scale of the roughness is exaggerated for illustrative purposes here) which can give rise to problems during device operation as previously alluded to.
  • an electrochromic device comprises a transparent electrode 1 - 4 , an ion storage layer 5 , an ion conductor (electrolyte) layer 6 , a layer of electrochromic material 7 and a further transparent conducting layer 8 .
  • a further layer 9 of transparent material such as glass or plastic would also typically be included.
  • an electrical potential is applied between transparent conducting layers 4 and 8 which causes redox reactions to occur in the electrochromic and ion storage layers 7 and 5 , with charge compensation by ion migration across the ion conductor layer 6 .
  • Li + ions are used in the ion conductor layer 6 .
  • the various layers may be deposited by techniques that are well known to a person skilled in the art, such as sputtering, PECVD (Plasma Enhanced Chemical Vapour Deposition) or solution deposition. Moreover the skilled person will be aware that some electrochromic devices may incorporate additional layers to those shown in this example.
  • the device incorporates a further interface layer 10 between the TCO layer 4 and the ion storage layer 5 .
  • interface layer comprises TiO 2 and its inclusion mitigates the problems associated with roughness of the TCO layer 4 .
  • an OLED device comprises a transparent electrode 1 - 4 , a hole injection layer (HIL) 11 , a hole transport layer (HTL) 12 , one or more emissive layers 13 , a hole blocking layer (HBL) 14 , an electron transport layer (ETL) 15 and a further electrode 16 .
  • HIL hole injection layer
  • HTL hole transport layer
  • HBL hole blocking layer
  • ETL electron transport layer
  • the device incorporates a further interface layer 10 between the TCO layer 4 and the HIL 5 .
  • interface layer comprises TiO 2 and its inclusion mitigates the problems associated with roughness of the TCO layer 4 .
  • a series of samples were prepared on 3.2 mm glass substrate. Each sample incorporated a stack of SiO 2 (example 9 only)/SnO 2 /SiO 2 /SnO2:F layers of varying thickness topped by an interface layer of TiO 2 , SnO 2 or SiO 2 . The samples are detailed in table 1 (layer thicknesses in Angstrom) along with an indication of observed sheet resistance and transmittance.
  • the stack interface layers were deposited by atmospheric pressure CVD.
  • a transparent conductive oxide was deposited on a glass substrate with the structure glass/SnO 2 (60 nm)/SiO 2 (15 nm)SnO 2 :F(720 nm). 25 nm of undoped tin oxide was deposited on top. Table 2 shows the properties with and without the additional undoped tin oxide layer. Surprisingly the sheet resistance of the coating is not substantially affected by the addition of a highly resistive layer
  • the TCO was used in a photovoltaic module resulting in an improved Voc and FF as shown in Table 3
  • the deposition was done using a ‘dynamic’ laboratory scale coater as illustrated in FIG. 4 .
  • the premixed precursors move towards the coater through a heated line 17 before they reach baffle section 18 which equalises the precursor flow before it enters the sealed coating section.
  • the glass substrate 19 sits on a heated carbon block 20 which is heated to the desired temperature using either heating elements (not shown) inserted inside the carbon block or by an induction coil (not shown) around the sealed coating section. Any unreacted precursor or by products are then directed towards fish tail exhaust 21 and continue towards the incinerator 22 .
  • the arrows show the direction in which the gaseous mixture moves.
  • the reactants (DEZ and t-butyl acetate) were delivered by passing N 2 carrier gas through bubblers (not shown).
  • the DEZ and t-butyl acetate bubbler temperatures were 100° C. and 85° C. respectively. Reactant quantities are expressed in terms of the total gas flow that reaches the substrate surface.
  • Example 16 was done ‘on-line’ by atmospheric pressure CVD, on a float glass ribbon produced during the float glass manufacturing process.
  • a thin film evaporator as described in U.S. Pat. No. 5,090,985 was used to deliver the reactants, whose quantities are again expressed as a percentage of total gas flow.
  • Table 4 summarises the reaction conditions used to generate examples 11-16.
  • SLPM Standard Litres per Minute
  • TEC10FSTM and TEC10TM are Nippon Sheet Glass Group products comprising coated glass substrates providing a transparent conducting electrode based on a fluorine doped tin oxide.
  • Table 5 summarises, for examples 11-16, measured values for ZnO thickness (in Angstrom), percentage haze, percentage visible transmission (Tvis), and sheet resistance of the sample Rs.
  • the transmission levels for all of examples 11-16 indicate that the addition of a Zinc oxide layer has not caused any significant absorption.
  • Haze levels on the silica coated substrates indicate an inherently smooth coating, and the roughness levels when coated on TEC 10 are similar to the substrate values.
  • Sheet resistance has been increased slightly by the over coat, but still in the range suitable for PV devices.

Abstract

Transparent conducting electrodes incorporate an interface layer located on the transparent conducting oxide (TCO) layer of the electrode. The interface layer offers a suitable surface for deposition of further layers in order to fabricate electronic devices such as electrochromic devices or organic light emitting diodes. Problems such as pinholes and short circuiting, associated with the inherent roughness of the TCO layer, are reduced.

Description

  • The invention concerns an interface layer for incorporation in devices produced on a transparent, electrically conducting electrode.
  • A number of electrical devices are known which are concerned with the generation or modification of light and which comprise an active region located between two essentially planar electrodes. In order to facilitate light transmission from (or to) the device, at least one electrode must be transparent.
  • Such devices include organic light emitting diodes (OLED) and electrochromic devices.
  • In OLEDs, an emissive electroluminescent layer comprising one or more layers of organic compound is located between the electrodes and emits light in response to an applied voltage.
  • In electrochromic devices a stack of materials which, in combination exhibit electrochromic properties is located between the electrodes and changes colour and, or opacity in response to an applied voltage.
  • Devices of the type which concern the invention are typically fabricated by providing a transparent conducting electrode comprising a transparent substrate and a conductive coating stack, and building successive layers thereon comprising the active region of the device and a further electrode—which may also be transparent. The transparent conducting electrode is frequently realised by depositing the conductive stack of coatings on the substrate using techniques such as chemical vapour deposition (CVD), which are well known to persons skilled in the art, see for example U.S. Pat. No. 7,968,201.
  • The conductive stack typically comprises a Transparent Conducting Oxide (TCO), i.e. a doped metal oxide, as the uppermost layer (i.e. the furthest layer from the substrate). In addition to offering the requisite electrical properties and mechanical stability, the TCO should offer a suitable surface for deposition of further layers as the rest of the device is fabricated. Examples of transparent conductive oxide materials include fluorine doped tin oxide (SnO2:F), Zinc oxide doped with Aluminium, Gallium or Boron (ZnO:Al, ZnO:Ga, ZnO:B), Indium oxide doped with tin (ITO) and cadmium stannate.
  • Unfortunately, these surfaces can be inherently rough which can cause localised short circuits drawing current from an area up to a few millimetres from the point of short circuit. This results in a undesirable aesthetic effect as well as reducing the performance of the device.
  • Furthermore defects such as pinholes in the devices deposited on the TCO can result in similar problems.
  • The current invention addresses both of these problems.
  • According to the invention a transparent electrode comprises the features set out in claim 1 attached hereto.
  • The inventors have shown that incorporation of a thin interface layer between the top of the electrode stack (TCO) and the active region of the device overcomes problems associated with roughness of the TCO. Examples of interface layer materials include TiO2, SiO2, SnO2 and ZnO and mixtures comprising any of these. The good device performance obtained when such interface layers are included is surprising because these materials have high electrical resistance.
  • In a preferred embodiment, the interface layer comprises a TiO2 layer having a thickness greater than 5 nm.
  • In another preferred embodiment, the interface layer comprises ZnO, having a thickness between 25 and 80 nm.
  • In a further preferred embodiment, the TCO layer comprises a fluorine doped tin oxide.
  • In some embodiments, the underlayers comprise a layer of SnO2 and a layer of SiO2.
  • The transparent conducting electrode according to the invention is suitable for incorporation in electronic devices such as electrochromic devices and organic light emitting diodes.
  • According to a second aspect of the invention, a method of manufacturing a transparent conducting electrode comprises the steps set out in claim 8 attached hereto.
  • In a preferred embodiment, the underlayers, TCO and interface layer are deposited by Chemical Vapour Deposition (CVD). The CVD may be done on the float glass ribbon produced during the float glass production process.
  • In another preferred embodiment, the underlayers, TCO and interface layer are deposited by Plasma Enhanced CVD.
  • In another preferred embodiment, the underlayers, TCO and interface layer are deposited by sputtering.
  • Preferably, the interface layer is selected from TiO2, SiO2 and ZnO. More preferably, the interface comprises TiO2 having a thickness of less than 5 nm.
  • In another preferred embodiment, the interface layer comprises ZnO, having a thickness between 25 and 80 nm.
  • In some embodiments, the TCO layer comprises a fluorine doped tin oxide.
  • In some embodiments, the underlayers comprise a layer of SnO2 and a layer of SiO2.
  • Materials such as TiO2 and ZnO are is rendered more hydrophilic upon exposure to ultraviolet (UV) radiation. Such treatment of interface layers according to the invention renders the electrode more receptive to deposition of subsequent layers as the device is fabricated, particularly where such layers are deposited by so-called ‘wet’ chemical methods i.e. techniques involving liquid solutions.
  • In another aspect of the invention, use, as a transparent conducting electrode, of an electrically conducting coating stack located on a transparent substrate;
  • the stack comprising at least one underlayer and a transparent conducting oxide (TCO) layer located on the underlayers,
    is characterised by the electrode having an interface layer located on the transparent conducting oxide layer.
  • The invention will now be described with reference to the accompanying figures in which:
  • FIG. 1 shows a transparent conducting electrode of the prior art;
  • FIG. 2 shows an electrochromic device incorporating a transparent conducting electrode according to the invention
  • FIG. 3 shows an organic light emitting diode incorporating a transparent conducting electrode according to the invention and
  • FIG. 4 illustrates a so-called ‘dynamic coater’ used for laboratory scale chemical vapour deposition of coatings on a substrate.
    •
  • All of the figures are for illustrative purposes only and the relative thicknesses of the layers are not to scale.
  • Referring to FIG. 1, a transparent conducting electrode of the type concerned by the invention typically comprises a glass substrate 1 bearing a conductive stack of coatings 2, 3 and 4. In the example shown, based on NSG's TEC™ series of coated glass, the stack comprises underlayers of SnO 2 2 and SiO 2 3 and a TCO layer 4 of SnO2:F.
  • The TCO layer 4 typically has a rough surface (although the scale of the roughness is exaggerated for illustrative purposes here) which can give rise to problems during device operation as previously alluded to.
  • Referring to FIG. 2, an electrochromic device according to the invention comprises a transparent electrode 1-4, an ion storage layer 5, an ion conductor (electrolyte) layer 6, a layer of electrochromic material 7 and a further transparent conducting layer 8. A further layer 9 of transparent material such as glass or plastic would also typically be included.
  • During operation, an electrical potential is applied between transparent conducting layers 4 and 8 which causes redox reactions to occur in the electrochromic and ion storage layers 7 and 5, with charge compensation by ion migration across the ion conductor layer 6. Typically, Li+ ions are used in the ion conductor layer 6.
  • These reactions are accompanied by changes in colour/transmission of the electrochromic layer 7.
  • The various layers may be deposited by techniques that are well known to a person skilled in the art, such as sputtering, PECVD (Plasma Enhanced Chemical Vapour Deposition) or solution deposition. Moreover the skilled person will be aware that some electrochromic devices may incorporate additional layers to those shown in this example.
  • According to the invention, the device incorporates a further interface layer 10 between the TCO layer 4 and the ion storage layer 5. In this example interface layer comprises TiO2 and its inclusion mitigates the problems associated with roughness of the TCO layer 4.
  • Referring to FIG. 3, an OLED device according to the invention comprises a transparent electrode 1-4, a hole injection layer (HIL) 11, a hole transport layer (HTL) 12, one or more emissive layers 13, a hole blocking layer (HBL) 14, an electron transport layer (ETL) 15 and a further electrode 16.
  • During operation, a voltage is applied between the electrodes and electon-hole recombination in the region of the emissive layers give rise to excitons' (a bound state of the electron-hole combination) which on relaxation give rise to an emission in the visible region. Light thus generated exits the device through the transparent substrate 1.
  • According to the invention, the device incorporates a further interface layer 10 between the TCO layer 4 and the HIL 5. In this example interface layer comprises TiO2 and its inclusion mitigates the problems associated with roughness of the TCO layer 4.
    • EXAMPLES 1-9
  • A series of samples were prepared on 3.2 mm glass substrate. Each sample incorporated a stack of SiO2 (example 9 only)/SnO2/SiO2/SnO2:F layers of varying thickness topped by an interface layer of TiO2, SnO2 or SiO2. The samples are detailed in table 1 (layer thicknesses in Angstrom) along with an indication of observed sheet resistance and transmittance.
  • The stack interface layers were deposited by atmospheric pressure CVD.
  • TABLE 1
    Physical Properties of Transparent Electrodes with Interface Layers
    Example
    1 2 3 4 5 6 7 8 9
    Glass 3.2 mm 3.2 mm 3.2 mm 3.2 mm 3.2 mm 3.2 mm 3.2 mm 3.2 mm 3.2 mm
    SiO2 150
    SnO2 250 300 250 250 250 250 250 250 250
    SiO2 250 220 250 250 250 250 250 250 250
    SnO2:F 3400 2300 3400 7600 3400 3400 3400 3400 3400
    TiO2 400 200 200 100 50 200
    SnO2 1000
    SiO2 200
    Rs (ohm/sq) 13.6 20.0 13.6 6.0 13.6 13.6 13.6 13.6 13.6
    % T 84.5 65.1 77.3 74.2 82.6 84.1 81.1 85.3 77.3
  • Note that the resistivities of TiO2 and SiO2 are both in excess of 1 MΩ·cm. The transmission values are likely to change when these stacks are incorporated in an actual device as reflectance is affected by the adjacent layers.
    • EXAMPLE 10
  • A transparent conductive oxide was deposited on a glass substrate with the structure glass/SnO2(60 nm)/SiO2(15 nm)SnO2:F(720 nm). 25 nm of undoped tin oxide was deposited on top. Table 2 shows the properties with and without the additional undoped tin oxide layer. Surprisingly the sheet resistance of the coating is not substantially affected by the addition of a highly resistive layer
  • TABLE 2
    Coated side Sheet
    Tvis reflection Resistance Haze
    Reference 82.1% 10.0% 8.7Ω/□ 11.0%
    Tin oxide 81.2% 10.4% 8.7Ω/□ 11.5%
    buffer coated
  • The TCO was used in a photovoltaic module resulting in an improved Voc and FF as shown in Table 3
  • TABLE 3
    Normalised performance data for Photovoltaic
    Device incorporating Interface Layer
    Jsc Voc FF
    Reference 1.00 1.00 1.00
    Tin oxide 1.00 1.01 1.01
    buffer coated
    • EXAMPLES 11-16
  • A series of experiments were conducted to deposit ZnO layers on various substrate to further investigate the suitability of this material as an interface layer according to the invention.
  • For examples 11-15, the deposition was done using a ‘dynamic’ laboratory scale coater as illustrated in FIG. 4. In this apparatus, the premixed precursors move towards the coater through a heated line 17 before they reach baffle section 18 which equalises the precursor flow before it enters the sealed coating section. The glass substrate 19 sits on a heated carbon block 20 which is heated to the desired temperature using either heating elements (not shown) inserted inside the carbon block or by an induction coil (not shown) around the sealed coating section. Any unreacted precursor or by products are then directed towards fish tail exhaust 21 and continue towards the incinerator 22. The arrows show the direction in which the gaseous mixture moves.
  • The reactants (DEZ and t-butyl acetate) were delivered by passing N2 carrier gas through bubblers (not shown). The DEZ and t-butyl acetate bubbler temperatures were 100° C. and 85° C. respectively. Reactant quantities are expressed in terms of the total gas flow that reaches the substrate surface.
  • Example 16 was done ‘on-line’ by atmospheric pressure CVD, on a float glass ribbon produced during the float glass manufacturing process. In this case, a thin film evaporator as described in U.S. Pat. No. 5,090,985 was used to deliver the reactants, whose quantities are again expressed as a percentage of total gas flow.
  • Table 4 summarises the reaction conditions used to generate examples 11-16. SLPM=Standard Litres per Minute; TEC10FS™ and TEC10™ are Nippon Sheet Glass Group products comprising coated glass substrates providing a transparent conducting electrode based on a fluorine doped tin oxide.
  • TABLE 4
    DEZ bubbler t-butyl acetate Total gas
    % t-butyl flow bubbler flow flow Linespeed
    Sample % DEZ acetate (SLPM)* (SLPM) (SLPM) (inch/min) Substrate
    11 1 5 0.28 0.91 36 200 SiO2 coated
    glass
    12 1 10 0.28 1.82 36 200 SiO2 coated
    glass
    13 1.3 10 0.37 1.82 36 200 TEC10FS ™
    14 3 4 0.85 0.62 36 150 TEC10 ™
    15 3 4 0.85 0.62 36 150 SiO2 coated
    glass
    16 1.5 4 630 318 TEC10
  • Table 5 summarises, for examples 11-16, measured values for ZnO thickness (in Angstrom), percentage haze, percentage visible transmission (Tvis), and sheet resistance of the sample Rs.
  • ZnO
    Sample thickness % Haze % Tvis Rs
    11 246 0.33 92.1 —
    12 383 0.43 91.4 —
    13 416 3.25 86.0 10.65
    14 660 1.13 85.1 12.70
    15 800 0.26 85.3 —
    16 251 2.12 86.4 18.62
  • The transmission levels for all of examples 11-16 indicate that the addition of a Zinc oxide layer has not caused any significant absorption. Haze levels on the silica coated substrates indicate an inherently smooth coating, and the roughness levels when coated on TEC 10 are similar to the substrate values.
  • Sheet resistance has been increased slightly by the over coat, but still in the range suitable for PV devices.

Claims (21)

1-20. (canceled)
21. A transparent conducting electrode comprising an electrically conducting coating stack located on a transparent substrate, the stack comprising at least one underlayer and a transparent conducting oxide (TCO) layer located on the at least one underlayer, and wherein the electrode comprises an interface layer located on the TCO layer.
22. The electrode according to claim 21, wherein the interface layer comprises one or more materials selected from TiO2, SiO2, SnO2 and ZnO.
23. The electrode according to claim 22, wherein the interface layer comprises a TiO2 layer having a thickness greater than 5 nm.
24. The electrode according to claim 22, wherein the interface layer comprises ZnO, having a thickness between 25 and 80 nm.
25. The electrode according to claim 21, where the TCO layer comprises fluorine doped tin oxide.
26. The electrode according to claim 25, wherein the underlayers comprise a layer of SnO2 and a layer of SiO2.
27. The electrode according to claim 21, incorporated in an electrochromic device.
28. The electrode according to claim 21, incorporated in an organic light emitting diode.
29. A method of manufacturing a transparent conducting electrode comprising the steps of:
depositing at least one underlayer on a transparent substrate;
depositing a layer of TCO on the underlayers; and
depositing an interface layer on the TCO.
30. The method according to claim 29, wherein the underlayers, TCO and interface layer are deposited by Chemical Vapour Deposition (CVD).
31. The method according to claim 30, wherein the underlayers, TCO and interface layer are deposited on a continuous glass ribbon during the float glass manufacturing process.
32. The method according to claim 30, wherein the underlayers, TCO and interface layer are deposited by Plasma Enhanced CVD.
33. The method according to claim 29, wherein the underlayers, TCO and interface layer are deposited by sputtering.
34. The method according to claim 30, wherein the interface layer is selected from TiO2, SiO2 and ZnO.
35. The method according to claim 29, comprising the step of depositing an interface layer of TiO2 to a thickness of greater than 5 nm.
36. The method according to claim 29, comprising the step of depositing an interface layer of ZnO to a thickness between 25 and 80 nm.
37. The method according to claim 29, where the TCO layer comprises fluorine doped tin oxide.
38. The method according to claim 37, wherein the underlayers comprise a layer of SnO2 and a layer of SiO2.
39. The method according to claim 29, further comprising the step of exposing the interface layer to ultraviolet (UV) radiation.
40. A method of utilizing an electrically conducting coating stack located on a transparent substrate as a transparent conducting electrode,
wherein the stack comprises at least one underlayer and a transparent conducting oxide (TCO) layer located on the underlayers, and
the electrode comprises an interface layer located on the transparent conducting oxide layer.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170336693A1 (en) * 2016-05-20 2017-11-23 Gentex Corporation Resistive coating for voltage uniformity
US20190165319A1 (en) * 2017-11-28 2019-05-30 Lg Display Co., Ltd. Light apparatus for organic light emitting device
US20210232014A1 (en) * 2019-12-22 2021-07-29 Jianguo Mei Electrochromic devices with increased lifetime

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9007674B2 (en) 2011-09-30 2015-04-14 View, Inc. Defect-mitigation layers in electrochromic devices
US11599003B2 (en) 2011-09-30 2023-03-07 View, Inc. Fabrication of electrochromic devices
US10802371B2 (en) 2011-12-12 2020-10-13 View, Inc. Thin-film devices and fabrication
CN107533267A (en) * 2015-03-20 2018-01-02 唯景公司 Switch low defect electrochromic more quickly
CN111665672B (en) * 2020-06-10 2023-03-21 宁波祢若电子科技有限公司 Dual-function electrochromic energy storage device and manufacturing method thereof

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6355353B1 (en) * 1999-03-09 2002-03-12 Nippon Sheet Glass Co., Ltd. Glass substrate having transparent conductive film
US20020181109A1 (en) * 2001-04-18 2002-12-05 Jau-Jier Chu Anti-reflection conducting coating with transparent conductive coating as outermost layer
US6551715B1 (en) * 1999-10-20 2003-04-22 Nippon Sheet Glass Co., Ltd. Glass sheet with conductive film and glass article using the same
US20040113146A1 (en) * 2002-09-03 2004-06-17 Brahim Dahmani Material for use in the manufacturing of luminous display devices
US20080047602A1 (en) * 2006-08-22 2008-02-28 Guardian Industries Corp. Front contact with high-function TCO for use in photovoltaic device and method of making same
US20080308151A1 (en) * 2006-11-02 2008-12-18 Guardian Industries Corp., Front electrode for use in photovoltaic device and method of making same
US20090155619A1 (en) * 2005-08-30 2009-06-18 Nelson Douglas M Light Transmittance Optimizing Coated Glass Article for Solar Cell and Method for Making
US20110100446A1 (en) * 2009-11-05 2011-05-05 Guardian Industries Corp. High haze transparent contact including ion-beam treated layer for solar cells, and/or method of making the same
US20120126273A1 (en) * 2009-07-06 2012-05-24 Arkema Inc. Oled substrate consisting of transparent conductive oxide (tco) and anti-iridescent undercoat
US8339031B2 (en) * 2006-09-07 2012-12-25 Saint-Gobain Glass France Substrate for an organic light-emitting device, use and process for manufacturing this substrate, and organic light-emitting device
US20130098435A1 (en) * 2011-10-17 2013-04-25 First Solar, Inc Hybrid contact for and methods of formation of photovoltaic devices
US20130174892A1 (en) * 2012-01-10 2013-07-11 Ppg Industries Ohio, Inc. Coated glasses having a low sheet resistance, a smooth surface, and/or a low thermal emissivity
US20140312327A1 (en) * 2013-03-12 2014-10-23 Ppg Industries Ohio, Inc. Transparent Conductive Oxide Coatings For Organic Light Emitting Diodes And Solar Devices

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101536608B (en) * 2006-09-07 2015-12-09 法国圣-戈班玻璃公司 For substrate, its Use and preparation method of organic light emitting apparatus, and organic light emitting apparatus
WO2009036284A1 (en) 2007-09-14 2009-03-19 Cardinal Cg Company Low-maintenance coatings, and methods for producing low-maintenance coatings
GB0811199D0 (en) * 2008-06-18 2008-07-23 Cambridge Entpr Ltd Electro-optic diode devices
US9007674B2 (en) 2011-09-30 2015-04-14 View, Inc. Defect-mitigation layers in electrochromic devices

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6355353B1 (en) * 1999-03-09 2002-03-12 Nippon Sheet Glass Co., Ltd. Glass substrate having transparent conductive film
US6551715B1 (en) * 1999-10-20 2003-04-22 Nippon Sheet Glass Co., Ltd. Glass sheet with conductive film and glass article using the same
US20020181109A1 (en) * 2001-04-18 2002-12-05 Jau-Jier Chu Anti-reflection conducting coating with transparent conductive coating as outermost layer
US20040113146A1 (en) * 2002-09-03 2004-06-17 Brahim Dahmani Material for use in the manufacturing of luminous display devices
US20090155619A1 (en) * 2005-08-30 2009-06-18 Nelson Douglas M Light Transmittance Optimizing Coated Glass Article for Solar Cell and Method for Making
US20080047602A1 (en) * 2006-08-22 2008-02-28 Guardian Industries Corp. Front contact with high-function TCO for use in photovoltaic device and method of making same
US8339031B2 (en) * 2006-09-07 2012-12-25 Saint-Gobain Glass France Substrate for an organic light-emitting device, use and process for manufacturing this substrate, and organic light-emitting device
US20080308151A1 (en) * 2006-11-02 2008-12-18 Guardian Industries Corp., Front electrode for use in photovoltaic device and method of making same
US20120126273A1 (en) * 2009-07-06 2012-05-24 Arkema Inc. Oled substrate consisting of transparent conductive oxide (tco) and anti-iridescent undercoat
US20110100446A1 (en) * 2009-11-05 2011-05-05 Guardian Industries Corp. High haze transparent contact including ion-beam treated layer for solar cells, and/or method of making the same
US20130098435A1 (en) * 2011-10-17 2013-04-25 First Solar, Inc Hybrid contact for and methods of formation of photovoltaic devices
US20130174892A1 (en) * 2012-01-10 2013-07-11 Ppg Industries Ohio, Inc. Coated glasses having a low sheet resistance, a smooth surface, and/or a low thermal emissivity
US20140312327A1 (en) * 2013-03-12 2014-10-23 Ppg Industries Ohio, Inc. Transparent Conductive Oxide Coatings For Organic Light Emitting Diodes And Solar Devices

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170336693A1 (en) * 2016-05-20 2017-11-23 Gentex Corporation Resistive coating for voltage uniformity
US10481460B2 (en) * 2016-05-20 2019-11-19 Gentex Corporation Resistive coating for voltage uniformity
US20190165319A1 (en) * 2017-11-28 2019-05-30 Lg Display Co., Ltd. Light apparatus for organic light emitting device
KR20190061588A (en) * 2017-11-28 2019-06-05 엘지디스플레이 주식회사 Light apparatus for organic light emitting device
US10892445B2 (en) * 2017-11-28 2021-01-12 Lg Display Co., Ltd. Light apparatus for organic light emitting device
KR102422061B1 (en) * 2017-11-28 2022-07-18 엘지디스플레이 주식회사 Light apparatus for organic light emitting device
US20210232014A1 (en) * 2019-12-22 2021-07-29 Jianguo Mei Electrochromic devices with increased lifetime

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